In this research, the types of hemicellulose that predominate in the leaves and tops of the three most cultivated varieties (CC 8475, CC 8592, V 7151) of sugarcane (Saccharum officinarum L.) in Valle del Cauca, Colombia were determined. Hemicellulose analyses were performed after delignification with sodium chlorite and extraction with 18% NaOH and 24% KOH containing 0.26 M NaBH4. The main components of hemicellulose were identified via FTIR and NMR spectroscopy, and monomeric sugars were identified via HPLC. Hemicellulose A composed of arabinoxylans, glucomannans and arabinogalactactans and hemicellulose B primarily composed of arabinoxylans were extracted. The hemicelluloses of the Colombian varieties were more stable against heat than those of the Venezuelan variety. The results of this project allowed discovery of the potential use of agricultural sugarcane residues for bioethanol production because they have a holocellulose content of more than 60%.